Pulping

The problem

Wood (this is what we have) Fibers (this is

what we want)
Lignin

Lignin is a major component

of the cell walls of plant cells
and a few types of algae.

Lignin is seen as the glue

that holds a tree together.
Compression woods, such as
conifers, are very rich in
lignin.

One quarter to one third of A small section of lignin

the dry mass of wood is made polymer.
up of lignin.
Composition of Common Pulpwood
(% mass)

Wood Cellulose Lignin

Aspen 56.5 16.3
Paper Birch 44.5 18.9
Red Maple 44.8 24.0
Balsam Fir 47.7 29.4
Jack Pine 45.0 28.6
White Spruce 48.5 27.1
Raw Material Preparation

Wood received in several different forms

As bolts (short logs) of roundwood with the bark still
attached
As chips about the size of a half-dollar that may have
been produced from sawmill, pre-chipped from
debarked roundwood elsewhere
As waste sawdust in the case of some pulping
processes.
1. Roundwood is first debarked then chipped if chemical
pulping is being done or are fed into a grinder in the
case of some mechanical pulps
2. Chips are screened for size, cleaned, and temporarily
stored for further processing.
Pulping (Fiber Separation)

Pulping means disintegration of bulky

fibrous material to small fibers.

The objective of pulping is to separate the

wood into individual fibers. The fiber
separation stage is the point at which the
several pulping technologies diverge.
Mechanical Pulping Processes:

The basic mechanical pulping processes:

1) Stone groundwood, (SGW)
2) Refiner, (RMP)
3) Thermomechanical pulping, (TMP)
4) Chemical mechanical, (CMP)
Mechanical Pulping
Mechanical pulping is the process by which
fibers are produced through mechanical
methods:
Grinding-Stone Groundwood (SGW)

Logs (very occasionally chips) are pressed into a

turning stone thus releasing fibers.
Refining-Refiner Pulp
Chips are fed between 2 disks. One disk is always
turning while the other can be fixed or turning.
Often heat or a chemical pretreatment is utilized.
 Raw Material Quality
Pulps cannot be brightened very much; therefore
good quality material must be used
Chips used should be less than 2 weeks old
(oxidation and biological decay darken chips after
this point).
Low bark and dirt tolerance (color and machinery
wear issues).
Species Dependence
Different wood species work better in different
processes.
Properties of Mechanical
Pulp
Relatively cheap
High yield of product (85-95%)
Low capital costs relative to Kraft mill
High opacity product
Large amount of fines in product scatter light
Allows printing on both sides of thin sheet
Good printing surface
Broad fiber size distribution gives smooth surface
Good bulk
Properties of Mechanical
Pulp
Relatively weak product
Not strong enough to get through printing press
Need to add chemical fibers to product
Can use recycle fibers
Limited brightness
Bleached with lignin retaining bleaching agents
Photo yellowing
Formation of chromophores from lignin
compounds through the reaction with light and
oxygen
Stone Groundwood: Equipment

Different designs.
Logs are pressed into a rotating stone.
The fibers are washed off the stone with water (cools the
stone).
Running this system under a slight pressure improves the process.
Pressure Grindwood (PGW)
Similar as SGW:
By pressurizing the wood with steam at
temperatures of 105-125C , the wood is heated
and softened prior to the grinding process.
This gives better separation of fibers with less
cutting action and lower fines generation.
This process yields a pulp that has higher tear
strength and freeness and is brighter than SGW.
Lower power requirements.
Refiner Mechanical Pulp
(RMP)
Chips are used.
Power requirements are 1600-1800 kWh/ton.
Disk refiners are up to 1.5 m in diameter and rotate at
1800 rpm with 60 Hz power; this gives a velocity at the
periphery of up to 140 m/s.
The plates containing the metal bars must be replaced
every 300-700 hours or low quality pulp is produced and
energy use increases.
Refining is usually carried out in two stages. The first is at
20-30% consistency to separate the fibers, while the
second is at 10-20% consistency to alter the surface of
the fibers for improved fiber bonding in the final paper.
Thermo-Mechanical Pulp (TMP)

Most important mechanical pulping method.

The TMP process is very similar to the RMP process
except that pulp is made in special refiners that are
pressurized with steam in the first stage of refining.
First stage: Elevated T (110-130C, just below the
glass transition temperature of lignin 140C, enhance
fibrillation) & P. second stage: Ambient T, P
Higher pulp strength. Energy req. 1900-2900 kWh/ton
An even consistency of 20-30% is ideal
The pulp yield is 91-95%
Chemi-Mechanical Pulping
(CMP)
C before SGW, PGW, RMP or TMP.
The grinding requirements were about half
that required without pretreatment and the
CSF was 300-350 ml.
2 stage: Chemical Pretreatment +
Mechanical
pulping
Chemical Pretreatments:
Hot sulfite: brighter, low strength
Cold soda: drains faster, coarse fiber,
CHEMICAL PULPING

Chemicals are used to reduce wood chips

into fibers.
This process separates each fiber from its

bonding materiallignin.
The adhesive qualities of lignin holds cellulose
fibers together.
 KRAFT PROCESS (sulfate
process)
German wordKraft meaning paper
Most popularly used process.

This is an alkaline process.

Is an industrial process for conversion

ofwoodintowood pulpconsisting of almost

purecellulosefibers
Na2SO4 is added to the cooking liquor. So its common

name is sulfate process.

The presence of sodium sulfide makes bleaching of pulp

easier and the paper produced has better strength.

Treatment of wood chips with a mixture ofsodium

hydroxideandsodium sulfide, known asliquor, that

breaks the bonds that linkligninto the cellulose
The Kraft (Sulfate) Process
The Kraft Process accounts for approximately 80% of wood pulp
production.
It is a cyclical process that is nearly self-sustaining due to recovery
and reuse of the inorganic chemicals used and a recovery boiler.
Cellulose is separated from the wood and made into pulp while the
lignin is concentrated into a waste product called black liquor.
Black liquor is concentrated using a multiple effect evaporator. Rosin
soap is skimmed off and used to manufacture Tall Oil.
The inorganic parts of the black liquor are used to regenerate the
sodium sulfide and sodium hydroxide that is used for pulping.
The organic parts, including the lignin, are burned in a recovery
boiler to provide energy to help run the pulping mill.
Approximately 7 tons of black liquor are produced for every ton
of pulp.
Chemical reactions involved
STEPS INVOLVED IN KRAFT PROCESS

Impregnation
Cooking
Recovery process
Blowing
Screening
Washing
Bleaching
Process chemicals
 IMPREGNATION
Common wood chips used are 1225
millimeters long
Prestreamed and wetted to impregnate
the chips with white liquor
White liquor contain NaOH+NaSH
COOKING
enters the digester below 100 C (212
F).
Typically delignification requires several
hours at 170to176C (338to 349F).
The combined liquids, known as black
liquor contain lignin fragments,
carbohydratesfrom the breakdown of
hemicellulose,sodium carbonate,
sodium sulfateand other inorganic salts.
Kraft Process

Reactor Pulp
Wood (350oF) Washer
Dissolve all
lignin
NaOH carbohydrates
Na2S
in water Evaporate
Steam
water
Steam
Furnace
Excess steam (dry paper)

Excess electricity
Chemical reactions involved

Digestion (hydrolysis and solubilization of

lignin)

R-R + NaOH RCOONa + ROH

R-R + Na2S Mercaptans
 Chemical recovery from black liquor

(a) Smelting

2NaR + air Na2CO3 + CO2

(lignin)
Na2SO4 + 2C Na2S + 2CO2
(from R) (white liquor)

(b) Causticizing

Na2CO3(aq) + Ca(OH)2(s) 2NaOH(aq) + CaCO3(s)

(green liquor) (white liquor)

CaCO3 CaO + CO2

CaO + H2O Ca(OH)2
RECOVERY PROCESS

Thermochemical sulfate reduction

1. Na2SO4+ 2 C Na2S + 2 CO2

Calciumcarbonateprecipitates from
white liquor
2. Na2S + Na2CO3+ Ca(OH)2 Na2S + 2 NaOH + CaCO3
Calcination
3. CaCO3 CaO + CO2
Slaking

4. CaO + H2O Ca(OH)2

Blowing cooked wood chips are
blown by reducing the
pressure to atmospheric
by release of steam
Screening Screening of the pulp
after pulping is a process
whereby the pulp is
separated from
largeshives,knots, dirt
and other diffusers
Pressure debris
Washing Atmospheric diffusers
Vacuum drum washers
Drum displacers
Wash presses
Process chemicals
Process chemicals are added to
improve the production process:
Surfactantsmay be used to improve
impregnation
Anthraquinoneis used as a digester
Anemulsion breakercan be added in
the soap separation
Defoamersremove foam
Dispersing agents,detackifiersand
complexing agentsare keeping the
system cleaner
Fixation agentsare fixating finely
dispersedpotential deposits to the
fibers
Bleaching

In bleaching tower
the pulp are
bleached to a high
brightness
Bleaching
Removal of colored residual lignin from
chemical pulp (usually kraft)
Increase brightness
Improve cleanliness
Improve brightness stability

Remove hemicellulose
Remove extractives

while preserving the strength (cellulose

integrity) and carbohydrate yield (cellulose
and hemicellulose) of the unbleached fiber
Bleaching
Lignin imparts a color to the raw pulp (hence its
name brown stock) and unless removed, will
continue to darken with age (note the yellowing,
Darkening )
Bleaching by removing the lignin gives higher

brightness to the paper than is possible by

leaving the lignin in the pulp and brightening by
decolonization, and also leads to a more durable
and stable paper.
 Dark color of unbleached pulp is due to
residual lignin, which remains in the pulp
because of its
1. high molecular weight
2. hydrophobic nature
3. chemical bonds to carbohydrates
Bleaching Chemistry
Bleaching chemicals
1. break up the lignin molecule
2. introduce solubilizing groups into the
fragments
3. disrupt lignin-carbohydrate bonds,
allowing fragments to dissolve
Bleaching of high-yield chemical pulps is
achieved by decolonizing with either an
oxidizing agent (combines oxygen) or a
reducing agent (combines hydrogen).
Bleaching Agents
Chlorine gas, sodium hypochlorite,
chlorine dioxide, oxygen gas, and hydrogen
peroxide are oxidants.

Sodium hydrosulfite is a reductant.

Alkali is used to remove the solubilized lignin

from the cellulose. Each has its advantages,
disadvantages, and limitations
Bleaching Sequences
A combination of bleaching and extracting
treatments is generally used for bleaching
chemical pulps.
The bleaching chemicals and the order in
which they are used make up the
bleaching
sequence.
The pulp and paper industry has developed a
series of shorthand descriptors for the multistage
bleaching sequences. The following abbreviations
are used to designate the bleaching agents:
CChlorination
E Extraction with sodium hydroxide
H Hypochlorite (sodium or calcium)
D Chlorine Dioxide
P Hydrogen Peroxide
O Oxygen
N Nitrogen dioxide
Z Ozone

CEDED CEHDED
Assessing Lignin Content and
Pulp Bleachability
1) Permanganate (K) number
2) Kappa number

Standard procedures have been established for

both bleaching indices. Both are based on the
amount of potassium permanganate that can react
with dry pulp samples. Most modem pulp mills
now use automated, continuous oxidation reduction
measurements or optical devices such as
brightness meters for on-line measurements to
gauge the progress of delignification and the need
for additional bleaching.